Fluorine-containing azo compounds



Fatented July 25 1956 Joseph B. Dickey, Rochester, N. Y., assignor to EastmanK-odak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application November 28,1945,

- Serial No. 631,468

'7 Claims. (01. zoo-207.5)

invention relates to new azo compounds and their application to the art of coloring.

I have discovered that the azo compounds having the general formula:

R=N=N- -R1 wherein R represents-a member selected from the group consisting of a benzene nucleus, a naphthalene nucleus, a benzothiazole nucleus and an azobenzene nucleus and R1 represents a member selected from the group consisting of a henzene nucleus and a naphthalene nucleus and wherein the member R1 contains a nuclear amino group which is substituted with an aliphatic hydrocarbon group containing a difluorinated carbon atom, constitute a valuable class of dye compounds. Depending upon their structure, the azo compounds of the invention possess application for the coloration of organic derivatives of cellulose, nylon, wool and silk. They yield dyeings having excellent light fastness.

While my invention relates broadly to the azo compounds having the formula above given, it relates more particularly to those compounds wherein R. and R1 are monocyclic benzene nuclei and especially to those compounds wherein R and R1 are monocyclic benzene nuclei containing no nuclear sulfonic acid or carboxylic acid group and R contains a nitro group directly attached thereto'ln para position to the azo bond.

Both sulfonated and non-sulfohated compounds are included within the scope of my invention. The nuclear non-sulfonated compounds "are of value for the coloration of organic derivatives of cellulose, especially cellulose acetate "rayon, and nylon and itis to 'these compounds and their application for the'coloration of organic derivatives of cellulose and nylon textile materials that my invention is particularly directed. The nuclear non-sulfonated compounds likewise possess some application for the dyeing of wool and silk. In general,'the monoazo compounds wherein R and 'R1- are monocyclic benzene nuclei free from nuclear sulfonic acid and carboxylic acid groups and wherein R contains a nitro group directly attached thereto in para position to the azo bond are especially advantageous for the coloration of organic derivatives of cellulose.

The nuclear sulfonated compounds .of my invention have little or noutility for the coloration of organic derivatives of cellulose but, possess application for the coloration of Wooland silk. Red, orange, .orangeeyellow, brownish-red, bluegreen, blue, rubine and violet shades, for example, can be obtained employing the dye com pounds of the invention.

It is an object of my invention to provide a new class of azo compounds suitable for the coloration of organic derivatives of cellulose, nylon, wool :and silk. Another object of my invention is to provide a process for the coloration of organic derivatives of cellulose, nylon, wool and silk. A further object isv to provide colored textile materials which are of good fastness to light and washing. A particular object is to provide a new class of nuclear non-sulfonated azo compounds suitable for the coloration of cellulose acetate rayon. Another particular object is-to provide colored cellulose acetate textile materials which are of good fastness to light and washing. A still further object is to provide a satisfactory process for the preparation of the azo compounds of my invention. Other objects will appear hereinafter.

Typical organic derivatives of cellulose include the hydrolyzed as well as the unhydrolyzed cellulose organic acid esters such as cellulose acetate, cellulose formate, cellulose propionate, or cellulose butyrate and the hydrolyzed as well as the unhydrolyzed mixed organic acid esters of cellulose, such as cellulose acetate-propionate, cellulose acetate-butyrate, and the cellulose others such as methyl cellulose, ethyl cellulose, or benzyl cellulose. While the use of the compounds of my invention will be illustrated more particularly in connection with the coloration of cellulose acetate rayon, a material to which theinvention is especially adapted, it will be understood that it applies to the coloration of the other materials mentioned herein.

The azo compounds of my invention can be prepared by coupling 'diazotized arylamines of the benzene and naphthalene series, diazotized .aminobenzothiazoles and diazotized aminoazo- 'benzenes with a coupling component of the benzene and naphthalene series containing a nu- Example 1.1 (at-nitrophenylazo) 4-(N-p-hydroxyethyl-N-difluoroethyl-aminobenzene amour:

. .CHQCHSOH 13.8 grams of p-nitroaniline are dissolved in 150 cc. of water and 25 cc. of 36% hydrochloric acid. The solution resulting is cooled to a temperature approximately -5 0. and the p-nitrcaniline is diazotized while maintaining thistem- 1 perature by the addition, with stirring, of a water solution of 6.9 grams of sodium nitrite.

20.1 grams of N-sehydroxyethyl-N-difiuoroethylaniline are dissolved in 200 cc. of cold dilute aqueous hydrochloric acid and the diazonium solution prepared as described above is gradually added with stirring. Following the addition of the diazonium solution the mixture resulting is stirred, while maintaining a temperatureof 0- 0., for about 30 minutes after which the coupling reaction which takes place is completed by neutralizing the hydrochIoric ,acid with sodium acetate. The dye compound formed isrecovered by filtration, washed with water and dried. It colors cellulose acetate rayon and nylon red shades.

Example 2.1-(2chl0ro 4 nitrophenylazo) 2- C HaCHzOH C1 OIEla 17.3 grams of o-chloro-p-nitroaniline are diazotized and the diazonium compound obtained is coupled with 21.5 grams of -N-,B-hydroxyethyl-N- difluoroethyl-m-toluidine. The diazotization, coupling and dye recovery operations can be carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate rayon and nylon rubine shades. 7

Example 3.1-(4 nitrophenylazo) -2 chloro-4- (N-fl-hydroxyethyZ-N-difluoroethyl) aminobenzene 13.8 grams of p-nitroaniline are diazotized and the diazonium compound obtained is coupled with 23.5 grams of N-B-hydroxyethyl-N-difluoroethyl-m-chloroaniline. The diazotization, coupling and dye recovery operations can be carried out in accordance with the procedure described in Example 1. The dye compound, obtained colors cellulose acetate rayon and nylon orange shades.

CH2CHF2 CHiOHzOH mesa Example 4.1-(2,4-ditrifluoromethylphenylazoi e 2-methyl-4-(N [3 hydrpmyethyl N difloroethyl) -aminobenzene 22.9 grams of 2,4-ditrifiuoromethylaniline are diazotized and the diazonium compound obtained is coupled with 21.5 grams of N-s-hydroxyethyl- N-difluoroethylm-toluidine. The diazotization, coupling and dye recovery operations can be carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate rayon and nylon rubine shades.

' Example 5.'-1-(4-acet0phenylazo) -2 methyl-4- N-difluoroethylamino-benzene 13.5 grams of p-aminoacetophenone are diazotized and the diazonium compound obtained is coupled with 25.1 grams of N-difiuoroethyl-mtolidin'e. The diazotization, coupling and dye recovery operations can be carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate rayon and nylon orange shades.

Emample s.-1 6 claim-0 2,4 dinitrophenylaao(- Z-acetamino-S-methoxy-el (N-fifl-dihydroxypropyZ-N-dzfluoroethyl) -aminobenzene '(A) 21.8 grams or 6-chloro-2,4-dinitroaniline are dissolved in 220 cc. of hot glacial acetic acid and the resulting solution is rapidly cooled to room temperature.

(B) 7 grams of sodium nitrite are dissolved in 53 cc. of sulfuric acid (sp. gr. 1.83) by heating the mixture to 70 0., and the resulting solution is then cooled to 15-20 C.

Solution (Al is added with stirring to (13) over a period of 30 minutes, while maintaining a temperature of 15-20 C. and the mixture resulting is then stirred for an additional hour at room temperature. v

31.8 grams of N-rm-dihydroxypropyl-N-difluoroethyl-5-acetamino 2 methoxyaniline are dissolved in cold dilute sulfuric acid and the di- Example 7.1 (2,6-dichloro-4-nitrophenylazo)- 2 chloro-4 -N,N di (2,2-difluoro-n-propyl) amino benzene C11 0 FaCHi 26.7 grams of 2,6-dichloro-4-nitroaniline fare *diazotized in known fashion. and the diazonium compound obtained is coupled in a dilute sulfuric acid solution, for example, with 28.3 grams of N,N-di (2,2-difiuoro-n-propyl)-m-chloroaniline. The dye compound obtained colors cellulose acetate rayon and nylon brownish-red shades.

Example 8.--1- (4-ni'trophenylazo) -4-N 2,2 difluorom-propy'laminobenzene 13.8 grams of p-nitroaniline are diazotized and the diazonium compound obtained is coupled with 17.1 grams of N-2,2-difluoro-n-propylaniline. The diazotization, coupling and dye recovery operations can be carried out in accordance with the procedure described in Example '1. The dye compound obtained colors cellulose acetate rayon and nylon red shades.

Example 9. 1- (4-nitrophenylazo) -4-N- (3,3 ai- I fluooo-n-b-utyl)-am.moben2ene 13.8 grams of p-nitroaniline are diazotized and the diazonium' compound obtained-is coupled with 18.5 grams of. NA3,3-difiuoro-n-butyl) -aniline. The diazotization, coupling and dye recovery operations can be carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate rayon and nylon red shades.

Example 10.-1-(4-1ritrophenyZazw-2 methotcy- 4-N-diflaoromethylaminobenzene 13.8 grams of p-nitreaniline are diazotized and the diazonium compound obtained is coupled'with 17.3 grams of N-difiuoromethyl-m-methoxy aniline. The diazotization, coupling and dye recovery operations can be carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate rayon and nylon red shades.

Example 11.1 (4 acetophenylazo) 4 (N-fimetltomyethyl-N-difluor0ethyl) -aminobenzene Example .12.-1-(2-cyano-4-nitrophehylazo) 4'- -=(N--4,5-dihyclrowyamyl-N-difluoroethyl) aminobenzene 14.7 grams of 1-amino-2-cyano-4-nitrobenzene are diazotized and the diazonium compound obtained is coupled with 25.9 grams of N-4,5-dihy- -droxyamyl-N-difiuoroethylaniline. The diazotization, coupling and dye recovery operations can be carried out in accordance with the precedure described in Example 1. The dye-compound obtained colors cellulose acetate rayon and nylon rubineshades.

Example 13.-1'-"(4-propionylphenyla2o) -4- (JV-El phosphatoethyl N -difluoroethyl) -aminobengene 114:9 grams 10f 1-amino-?i-propionylbenzene are diazotized and the 'diazonium compound obtained is coupled with'2812 grams ofN-B-phosphatoethyl- N-difiuoroethylaniline. The coupling reaction can be carried out in a cold dilute sulfuric acid 'o'rhydrochloric acid solution. "The dye compound obtained colors cellulose acetate rayon and nylon orange shades. The formula given for the compound is that for its free acid form. As will be understood by those in the art to whom this inyention is directed, the dye, depending upon its method of recovery, can be obtained in either the free acid or salt formsuch as the sodium, potassium or ammonium salt form.

Example -14.--1- (4-nitrophenylazo) -2 methyZ-4- (methyl ester of N -c-carboxyethyl-N -diflaoroethyl) amz'n'obenzene 13.8 grams of p-nitroaniline are diazotized and the diazonium compound obtained is coupled with 25.7 grams of the methyl ester of N-p-carboxyethyl-N-difluoroethyl-m-toluidine. The diazotization, coupling-and dye recovery operations can be carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate rayon and nylon orange-red shades.

By the use of 27.1 grams of the ethyl ester of N p carboxyethyl N difiuoroethyl m to'luidine in the foregoing example a dye compound is obtained which similarly colors cellulose acetate rayon and nylon orange-red shades.

CHzCHFz Ewample 15.-1 (4 nitrophenylazo) 4 (N cyanoethyl-N-difiuoroethyl) -amz'nobenzene 13.8 grams of p-nitroanilineare diazotized and the diazonium compound obtained is coupled with 18.2 grams of N-cyanoethyl-N-difiuoroethylaniline. The diazotization, coupling, and dye recovery operations can be carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate rayon and nylon orange shades.

Example 16'.1 (2,4 dinitro 6 N ethylsulfamylphenyllaeo) 4 (N c hydromypropyl- N dz'fluoroethyl) aminobenzene omcnonom NO 1 N=NON/ H \C-H2OHF2 O2N/ OrHa 29.2 grams of 1-amino-6-N-ethylsulfamyl-2,4- di-nitrobenzene are diazotized and the diazonium compound obtained is coupled with 21.5 grams :of. N p -:hydroxyprQpy1- N-difluoroethylaniline. The diazotization, coupling and dye recovery operations are, carriedout in accordance with the procedure described in Example 6. The dye compound obtained colors cellulose acetate rayon and nylon violet shades.

Example 1?.--1 (,4 nitrophenylazo) 4 [(N,N dz) dz'fluoroethyll aminobenzene 13.8 grams of p-nitroaniline are diazotized and coupled with 22.1 grams of [(N,N-d1) -difluoroethyll-aniline. The diazotization, coupling and dye recovery operations can be carried out in accordance with the procedure described in EX- ample l. The dye compound obtained colors cellulose acetate rayon and nylon orange shades.

Example 18 GHSO 011,011,011

amour,

18 grams of 2-amino-G-methoxybenzothiazole are diazotized in known fashion (in a formic acid medium, for example) and the diazonium compound obtained is coupled in a dilute hydrochloric acid medium with 20.1 grams of N-fi-hydroxyethyl-N-difluoroethylaniline. The dye compound obtained colors cellulose acetate rayon and nylon red shades.

Example 19 19.4 grams of 2-amino-5-ethoxybenzothiazole are diazotized and coupled in an acid medium with 20.7 grams of N-difiuoroethyl-c-naphthylamine. The dye compound obtained colors cellulose acetate rayon and nylon rubine shades.

Example 7 20 19.7 grams of p-aminoazobenzene are diazo tized and the diazonium compound obtained is coupled in an acid medium with 21.5 grams of N ,3 hydroxyethyl N difiuoroethyl m toluidine. The dye compound obtained colors cellulose acetate rayon and nylon red shades.

CHaCHaOE CHHCHFZ Example 21 CHzCHaOH OHROHFQ 14.3 grams of a-naphthylamine are diazotized and the diazonium compound obtained is coupled with 23.5 grams of N-,o-hydroxyethyl-N-difiuoroethyl-m-chloroaniline. The diazotization, coupling and dye recovery operations can be carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate rayon, nylon and silk yellowishorange shades.

- Example 22 13.8 grams of p-nitroaniline are diazotized and the diazonium compound obtained is coupled in a slightly acid medium with 22.3 grams of 5-hydroxy 1 difiuoroethylaminonaphthalene. The dye compound obtained colors cellulose acetate rayon, nylon and silk violet shades.

Example 23 H NO N=N N-GHaOHF:

SOaH

21.8 grams of 1-amino-2-sulfonic-4-nitrobenzene are diazotized in known fashion and the diazonium compound obtained is coupled in an acid medium with 20.7 grams of N-difluoroethyla-naphthylamine. The dye compound obtained colors silk, wool, and nylon rubine shades.

Example 24 /CH5CHOHCH2OH 22.3 grams of l-amino-Z-sulfonic naphthalene are diazotized and the diazonium compound obtained is coupled in an acid medium with 25.8 grams of N-fl,'Y-dihydroxypropyl-N-difluorobutylaniline. The dye compound obtained colors silk,

wool and nylon orange shades.

Example 25 H N-CHzCHFa HOaS N=N 30.1 grams of 1-amino-2,4-disulfonicnaphthalene are diazotized and the diazonium compound obtained is coupled in an acid medium with 20.7

grams of N-difluoroethyl-a-naphthylamine. The

Tabulation A.Continued Amine Coupling Component Color 2 ,fi-djchloro 4-nitroaniline Reddish-brown to brownish-whine. fi-bromdZ-chloro--nitroaniline Do. 6fluoro-2-chloro--l-nitroaniline Do.

a-naphtyl'lmin P l-amiRQZ i-dinitronaphthalene l-amino-S-hydroxynaphthalene p-aminoazobenzene Yellow to orange. Orange to violet. Orange to rubine.

2'-cl11oro-4'-nitro-p-aminoazobenzene- 2-amino-fi-ethoxybenzothiazole 2-amino-5-rnethoxybenzothiaiole The compounds indicated in the following tabulation can be prepared following the procedure described in the examples given hereinbefore. They color cellulose acetate rayon and nylon the colors set forth.

ponents used in their manufacture is described hereinafter.

The benzene coupling components of the invention can be prepared by reacting a chlorobenzene compound with a difluoroalkylamine. If desired,

Tabulation B Amine Coupling Component Color p-nitrnanilinfl (1) E-hydroxy-l-difluoroethyleminonaphthalene Violet.

Do..- (2) fi-lliydroxy-l-(2,2-diiiuoron-propyl)-aminonaphtl1a- Do.

. ene. Do. (3) Z-ethoxy-l-difluoroethylamino-naphthalene Rubin Do (4) fi-ohloro-dhydroxy-l-difiuoroethylaminonaphtha- Violet.

. ene. Do (5) 6-bromo-5-l1ydroxy-l-(3,B-difiuoro-n-butyD-amino- Do.

i V naphthalene. p-aminoacetophenone Coupling Components 1-5 above Red. z-hydroxyi-nitrmn do Violet. 2-chloro-4-nitroaniline- D o-aminophenylmethyl-snlfonp 6-N-ethylsulfamyl-ZA-dinitioaniline p-aminoazobenzene a-naphthylamine 2,4dinitro-a-naphthylamine.

G-ethoxybenzothiazole- 5-methoxybenzothiazole Similarly, the compounds indicated in the following tabulation c'an be prepared following the procedure described in the examples given hereinbefore. They color silk, wool and nylon textile materials red, orange, orange-yellow, rubine and violet shades, for example.

a catalyst for the reaction such as powdered 7 benzene compound and a difluoroalkanol in the Tabulation presence of a metallic hydrogenation catalyst such Amine l-amlijnoi-nitro-2-sulionicbnzene o Do p-sulfanilic acid 1-amino-2-chloroi-sulfonicbenzene L-gmino-ZA-disnlfnninhon one D0, l-amino-Z-sulfonicnaphthaleue Do. l-amino-2-hydroxy-4-sulfonicnaphthalene. Do. 2-naphthylamine-8sulfonic acid D0.

Coupling Component (1) N-difluoroethylaniline. (2) N-difluoroethyl-N-fi-hydroxyethylaniline. (3) N-difluoroethyl-N-B-hydrowethyl-m-toluidine. g4) N -di.fluoroethyl-N-4,S-dihydroxyamylaniline.

,N-di)-difluoroethylaniline. (6) N-2,2-difluoro-n-propyl-N-B-hydroxyethylaniline. (7) N-2,%difluoro-n-propyl-N-fi,y-dihydroxypropy1m-toluidine. (8) -hydroxy-l-difluoroethylaminonaphthalene. (9) 1-difluoroethylaminonaphthalene. Coulgling Components 1 9 above.

as Raney nickel and other nickel catalysts, a

cobalt catalyst and copper chromite. A still further method by which the coupling compounds of the invention can be prepared is by reaction between an aminobenzene compound and a difluoroalkyl halide in the presence of an acid binding agent. Acid binding agents that can be used include, for example, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate and barium hydroxide. Each of these methods of preparation is illustrated hereinafter. Difluoroalkylamines that can be used in the preparation of the couplin compounds of my invention include, for example, 2,2-difluoroethyl- 7 amine (CI-IFaCHzNI-Iz), di-(2,2-difiuoro) -diethylbutylamine (CHzCFzCHzCHzNHz). Difluoroalkyt halides that can be employed. include, for example, BrCHFz, CICHFz, ClCI-IzCHFz,

BI'CI-IaCHFZ, ICHzCI-IFz, CICHzCFiCI-Is and CICH2CH2CF2CH3'. Difiuoroalkanol" com pounds that can be employed include; for ex-- ample, 2,2-difluoroethanol: (CHFzCHzOH).

n Ornomonm 28 grams of chlorobenzene,. 81 grams of 2,2- difluoroethylamine, 300 cc. of Water, 0.25. gram of copper powder and 0.25 gram of cuprous oxide are heated. together in. a copper lined, shaking autoclave at 220-225 C. for 2Q hours with shaking. When cool, the contents of the autoclave are removed and extracted with benzene. After drying, the benzene extract is fractionally distilled under reduced pressure to re-- cover N (2,2-difiuoroethyl) aniline and unree acted 2,2-difluoroethylamine, N-(2,2-difluor,oethyl) -aniline is a colorless liquid.

Using the procedure described in Example. A, and employing the proper chlorobenzene compound, thefollowing compounds. are. readily prepared:

N-difluoroethyl-o-chloroaniline N-difluoroethyl-o-toluidine N- difluoroethyl-m-toluidine N-difluoroethyl-o-ethylaniline N-difluoroethyl-2-methoxy-5-acetaminoaniline By the use of 2,2-difiuoro-n-propylamine, 3,3- difluoro-n-butyl'amine and di-(2,2'-difluoro) -diethylamine, respectively, in place of 2.2-difiuoroethylamine in Example A, N-(2,2-difluoro-npropyl) -ani1ine, N- (3,3-difiuoro-n-butyl) -anil'ine and N',N'-di(2,2-difluoroethyl) -ani1ine, respectively, are obtained. It will be understoodthat by the use of these amines, aniline compounds, in addition to aniline, containing a 2',2'-difiuoron-propyl group, a 3 ,3-difiuoro-n-butyl group and a di(2,2-difiuoroethyl) group on the nuclear amino group can be prepared. Thus, the following compounds, for example, can. be prepared? N 2,2 d'ifiuoro n propyl) 2 methoxy 5- methylaniline N (2,2 difluoro n propyl) m propionyl'- aminoaniline N- (3,3-difluoro-n-butyl) -m-toluidine N,N-di- (2,2-difluoroethyl) -m-ohloroaniline 47 grams of m-to'luidine, '74 grams of 2',2-difluoroethanol and 5 grams of Raney nickel" are heated together in a shaking autoclave for 25 hours. When cool, the contents of the autoclave are removed and' filtered to remove nickel and the filtrate is fractionated under reduced pressure, (6 mm., for example). N-(2-,2'-di'- fluoroethyD-m-toluidine is obtained in a good yield.

Using the procedure described in Example B, the following compounds are readily prepared:

N'-difluoroethyl-o-fiuoroaniline N-difiuoroethyl-o-anisidine N-difluoroethyl-2-methoxy-5-methylani1ine N-difluoroethyl-m-n-butyrylaminoaniline aniline 15' grams of 2,2-difiuoroethylbromide, 13.8 grams'of o-chl'oroaniline and 6 grams of sodium carbonate are placed a suitable reaction vessel and heated under refluxing conditions until carbon'dloxide ceases to be evolved. Upon cooling, the reaction mixture is extracted with ethyl alcohol and the ethyl alcohol extract is fractionated under reduced pressure (2 mm., for example) to give a good yield of N-(2,2-difluoroethyli-o chloroaniline.

15.7 grams of N-difluoroethyl-m-toluidine, 15 grams of difiuoroethylbromide and 6 grams of sodium carbonate are placed in a suitable reaction vessel andheated under refluxing conditions until carbon dioxide ceases to be evolved. The reaction productv is extracted with ethyl alcohol and the: ethyl alcohol extract is fractionated under reduced pressure (5 mm., for example) to give a good yield oi N,N-di-(difluoroethyl) -aniline.

Example. B.N-trifluaroethyl N difluoroethylaniline This compound is obtained by reacting N-difiuoroethyl aniline with 2,2,2-trifluoroethylbromide (CFaCI-IzBr) in accordance with the procedure described in Example D.

Example F.N-dz'flaoromet,hyZ-N-difluoroethylaniline This compound is obtained by reacting N-difluoro'ethylaniline with 2,2-difluoromethylbromide (BI'CHF'z) in accordance with the procedure described in Example D.

Example G.--N-c-methowethyl-N- dz'fluoroethylaniline This compound can be obtained by reacting N--13-methoxyethylaniline with 2,2-difiuoroethylbromide in accordancewith the procedure described in- Example D.

Following the procedure set forth in Examples C, D, E, F and G the following compounds, for example, are readily prepared:

The trifluoroethyl, the trifiuoropropyl; -'and :the trifiuorobutyl group can be introduced by reacting an aniline compound having a replaceable hydrogen atom on the amino group with an equivalent gram molecular weight of CFsCI-IaClOI' respectively, in accordance with the procedure set forth in Examples C, D, E, F and G.

15.7 grams of N-difluoroethylanilizie;- grams of ethylene oxide and 50 cc. of dioxane. are heated together with stirring in an autoclave at 180 C. for six hours. Upon cooling, the reaction mixture is removed from the autoclave and dis tilled under reduced pressure. A good yield of N-p-hydroxyethyl-N-difiuoroethylaniline is obtained.

Using the procedure described in Example H and employing the proper alkylene oxide, (trimethylene oxide, propylene oxide, glycidol, and e-methyl glycidol, etc.) the following compounds are readily prepared: i

Where a lW-dihydroxypropyl group or other group which will decompose if the compound is attempted to be distilled is present, the reaction mixture is removed from the reaction vessel, filtered if desired and the solvent material removed by distillation under reduced pressure, leaving the desired product as a residue of the distillation.

Example I .N-p-hydro:ryethyl-N -difluoroethylm-chloroaniline 19.1 grams of N-difiuoroethyl-m-chloroaniline, 5 grams of ethylene oxide and 50 cc. of dioxane are heated together with stirring in an autoclave at 180 C. for 6 hours. Upon cooling, the reaction mixture is removed from the autoclave and distilled under reduced pressure. A good yield of N-e-hydroxyethyl-N-difiuoroethyl-mchloroaniline is obtained.

Similarly by the use of 17.1 grams of N- difluoroethyl-m-toluidine in place of N-difiuoroethyl-m-chloroaniline, a good yield of N-,B- hydroxyethyl N difluoroethyl m toluidine is obtained.

Example J .-N ,Y dihydrowypropyZ-N -difluoroethyl-Z-methozcy-S-acetccminormilim 24.4 grams of N-difluoroethyl-2-methoxy-5- acetaminoaniline and 10.6 grams of sodium carbonate are mixed together and heated with stirring in a suitable reaction vessel in an atmosphere of nitrogen to 140 C. Then 12 grams of glycerolchlorohydrin (ClCHzCHOHCHzOH) are added drop by drop with stirring over a period of three hours, while maintaining the temperature at C. When carbon dioxide ceases to be evolved, the reaction mixture is extracted with acetic acid and the acetic acid extract is carefully fractionated under reduced pressure to remove the acetic acid. N-,Bfl-dihydroxypropyl-N- difluoroethyl 2 methoxy-5 acetaminoam'line is obtained as a dark, viscous product and is stored in a stoppered bottle.

Where the intermediate is to be used as a coupling component in the preparation of azo dyes the fractionation operation may be omitted and the acetic acid extract stored and used as such. If desired, the reaction mixture can be extracted with butyl alcohol and the desired product recovered by removing the butyl alcohol by distillation or evaporation.

The process described in Example J is broadly applicable. In place of the chlorohydrin used in the example ethylene chlorohydrin, trimethylene chlorohydrin, p-methyl-,8,'y-dihydroxypropylchlorohydrin, propylene chlorohydrinv and 1- chloro-2,3,4-trihydroxybutane, for example, can

be usedto obtain coupling compounds of the invention.

Using the procedure described in Examples H, I and J the following compounds, for example, are readily prepared:

N difluoroethyl N 5 hydroxyethyl acetaminoaniline N difiuoroethyl N p hydroxyethyl 2 methoxy-5-methylaniline N-difiuoroethyl-N-p-hydroxypropylaniline N difiuoroethyl N .5 hydroxypropyl In a toluidine N difluoroethyl N 3, dihydroxypropyl m-toluidine N difluoroethyl N 5, dihydroxypropyl m-chloroaniline N.-difiuoroethyl-N'y-hydroxypropylaniline N-difluoroethyl-N-delta-hydroxybutylaniline N difluoroethyl N delta hydroxybutyl m toluidine N-difluoroethyl N-2,3,4-trihydroxybutylaniline N-difluoroethyl-N-w-hydroxy-n-amylaniline N '-'2,2 difluoro n propyl N p hydroxy ethyl-m-toluidine N 2,2 difluoro n propyl N fiyy dihydroxypropylaniline N 2,2 difluoro n propyl N 2,3,4 tri hydroxybutyl-m-ethylaniline N 3,3 difiuoro n butyl N ,6 hydroxyethylaniline N 3,3 difiuoro n butyl N 4,5

amylanilinedihydroxy Example K.Meth1 l ester of N-fi-carboxyethyl- N-dz'fluoroethylamline 17.9 grams of the methyl ester of N-B-carboxyethylaniline, 15.1 grams of difluoroethylbromide and 6 grams of sodium carbonate are placed in a suitable reaction vessel and heated under refluxing conditions until carbon dioxide ceases to be evolved. Upon cooling, the reaction mixture is extracted with ethyl alcohol and the ethyl alcohol extract is fractionated under reduced pressure, 5 mm., for example, to give a good yield of the methyl ester of N-fl-carboxy-ethyl-N- difluoroethylaniline.

Using the procedure described in Example K, the following compounds are readily prepared:

Methyl ester of N fi carboxyethyl-N-difluoroethyl-m-toluidine i asraeoa 1'7 Methyl: ester of: N pbcarboxyethyleN-difluoroethyl-m-anisidine Methyl ester of N-p-carboxyethyl-N-2,2-difiuoron-propylaniline Methyl ester of N-pcarboxyethyl-N-3,3=difluoron-butylaniline By the use of an equivalent gramv molecular weight of the ethyl ester ofv N-p-carboxyethylaniline-for. the methyl ester of N-p-carboxyethylaniline, the corresponding ethyl ester compounds can be preparedi Example L.N-'y-ketobutyl N-difluoroethylaniline CHzCHEz Nf-yeketobutyli-Ne difluoroethylem-toluidinea N-y-ketobutyl N difiuoroethyl- 2r methoxy--5-' acetaminoaniline N-c-ketopropyl-N-difluoroethylaniline N-y-li'etoamyl-N-difluoroethylaniline N -y-ketobutyl N- (2;2 difluoro-n-propyl)-aniline N y-ketobutyl N- 3 ,3 -difiuoro-n-buty1 -ani1i'ne Example M-'.'-N-p-cyanoethyl-N difluoro'ethylanilinew 18 grams of N-difluoroethylaniline, grams of acrylonitrile and 2 cc. of'sulf'uric acid are placed in a suitable reaction vessel. and heated on a st'eam-bathfor several weeks. The sulfurict'acid is then carefully neutralized by the addition of sodium hydroxide and the" reaction mixture is: .fi'actionated; under reduced. pressure.v

A. good yield of Nedcyanoethyl Nedifiuoroethylaniline is obtained.

Using the procedure described in Example M, the following compounds are readily prepared:

N-fl-cyanoethyl-N- difluoroethyl-m-toluidine N-p-cyanoethyl-N (2,2-difluoro-n-propyl)-aniline N -;8-cyanoethyl-N- 3,3-difluoro-n-butyl) -aniline 28 grams of chlorobenzene, 170 grams of 6,6,6- trifiuorohexylamine, 300 cc. of water, 0.25 gram of copper powder and 0.25 gram of cuprous oxide are heated together in a copper-lined shaking autoclave at 220-225 C. for 24 hours with shaking. When cool, the contents of the autoclave are removed and extracted with benzene. After drying, the benzene extract is fractionally distilled under reduced pressure to recover N-(6,6,6- trifluorohexyD-aniline and unreacted 6,6,6-trifiuorohexylamine. 156 grams of 5,5,5-trifiuoroamylamine can be substituted for the 6,6,6-tri- "18 fiuorohexylamine of the example to obtaini N- (5;5;5T-trifluoroamyl)-aniline. 231: grams of: N-

-(6;6,6etrifluorohexyl)-aniline; 15:1- grams of difiuoroethylbromide and. 6. grams of. sodium carbonateaareplacediinfa suitablereaction vessel-and heated under refluxing conditions until carbon dioxide ceases to be evolved. The reactionproduct is extracted: with l ethyl alcohol and: the ethyl alcohol extractis' fractionated under reduced pressure (2 mm., for example) to give a good yield of N-(6,6,6-trifluorohexyl) N difluoroethylaniline. Similarly, by'the'use of 21.7 grams of N- (5,5,5-trifluoroa'myl) -aniline in the foregoing reaction, N-(5,-5,5-trifluoroamyl) -N-difiuoroethylaniline can be obtained. Using the procedure described hereinbeforegthe following compounds are readily prepared. N. e (5.55 trifluoroamyU- 'difiuoroethyl: zmetlioxy-5e-methylbenzenev N 7 5,5;5-trifluoroamyl) N diflllOIOBthYl-IflvtOlil- -idine I N; (5,5;5-trifluoroamylll i-- N'e (22-difi1ioro-n-propyl) aniline N'- 6',6,'6'-trifluorohexyl)' luidir'ie, I N-.(filfifietrifiuorohexyl)" tyU-aniIine v I I "The: N-difluorcalkylnaphthylamine coupling components of the invention can be preparedaby the general methods described in connection with the N-difiuoroalkylaniline coupling components. Thus a-naphthylami'ne' can be reactedwith 2,2- difiuoroethancl inaccordance with the procedure described in Example B to obtain N-difluoroethylmaphthylamine. a-Naphthylamine and lamino-5-hydroxynaphthalene, for example; can be reacted with 2,2-difiuoroethylbromide in. accordancerwith. the p'rocedure' described in Example D to obtain N-difluoroethyl-a-naphthylamine and 5v-hydroxyg ldifiuoroethylaminonaphthalene, respectively. Also c-chloronaphthalene can be reacted with a difluoroalkylamine in accordance with the procedure described finExample A to obtain an N-difiuoroalkyl-a-naphthylamine. Thus N-difiuoroethylwnaphthylamine', N-2,2-difiuoro-n-propyl-a-naphthy1amine and N 3,3-difluorot-n-butyli-anaphthylamineyfor" example; can beprepared r by'=reacting tachloronaphthalene.-with 2 ;2.-difiuoroethylamine; 2,=2:- difiuoroze rr propylamine-1 and BIKLdifluom-nbutylaminez respectivelyz" I From the foregoing it is believed that the manner of preparation of the N-difluoroalkylnaphthylamine compounds of my invention is clear to those skilled in the art to which this invention is directed and no further description of their preparation is thought necessary.

The azo compounds of my invention can be employed for the coloration of the materials named herein by the well known methods, employed by those skilled in the art, for the coloration of these materials.

N-difiuoroalkylaminobenzene compounds are described and claimed in my copending application Ser. No. 624,943, filed October 26, 1945. Reference may be had to this application for additional information concerning the preparation of these compounds.

N-trifiuoroalkylaminobenzene compounds are described and claimed in my copending applica" tion Serial No. 624,942, filed October 26, 1945. Reference may be had to this application for additional information concerning the preparation of these compounds.

N .difluoroethylg meto- 2,516,302 I v o :19 20 I H Azoxcompounds. contaim'ng an amino-"group 4; An azo compound having the general for- -whichvis substituted with analiphatichydroca'rmula: I V bon group containing a trifiuorinated carbon atom are described and claimed in my copending application Serial No; 631,469, filed November 28, 5 No 1945. l

I claim:

1. An azo compound free from nuclear sulfonic he fi n X represents a hal n t m, R repreand carboxylic acid groups having the general Sents a fi s ght chain alkyl 1 1 formula; having 2 to 4 carbon atoms and wherein said fluo- H x rine atoms are on a single carbon .atom and'Ri represents a hydroxyalkyl group having 2 to 5, R--N=N,-- inclusive carbon atoms.

l Y i I 5. The azo compound having the formula:

r Y 1' wherein R represents amono nitrated monocyclic benzene nucleus and wherein said nitrogroup is -O in para position to the azo bond, X represents a cmcmon member selected from thegroup'consisting of a 2,2,- difluoroethyl group, a 2,2-difiuoro-n-propyle 6. The azo compound having the formula:

group, a 3,3-difiuoropropyl group, a 3,3-difiuoroomonr:

n butyl group and a 4, i -difluorobuty1 group, Y Noe-ON: .QN/ represents a member selected from the group con- \CHACEO'H sisting of a hydrogen atom and ahydroxyalkyl $1 on; l

"gm-up having 2 to 5, inclusive, carbon atoms '7 The azo com und havin the formula: thereforand Zrepresents a member selected-from pg g the group consisting of a hydrogen atom, a chlo- 5 v rine atom andamethyl group. 0a -N=N N ";2'.'An azo compound having the general '-foro \QHaCmOH R JOSEPH B. DICK Y; O -REFERENCES CITED 1 1 The following references are-of record in the I M 1m of this patent: wherein R. represents a difluorinated straight m chain alkyl group having 2 to 4 carbon atoms and UNITED STATES PA S wherein said fluorine atoms are on a single carbon Number N Date -atom and R1 represents a hydroxyalkyl group 2,082,156 Fehx'et June 1937 av 2 td5inc1usive carbon atoms 40 2,118,661 Baumann May 24, 1938 1' 3. An azo compound having the general for- 24531318 Heyna et a1 4, 1939 v 2,173,417 Huber Sept. 19,1939 V y y r RV 2,194,927 Daudt etal. Mar. 2d,, 1940 a a T/ 2,408,421 Grimmel et al Oct. 1,1946 T O\ FOREIGNPATENTS T? t Number Country Date .-.wherein R; represents a' difluorinated straight 209,089 Switzerland June 17,1940

1-chain alkylgroup having2 to 4 carbon atoms l and wherein said'fluorine atoms are on a. single OTHER, REFERENCEs v carbon atom and R1 represents a hydroxyalkyl a Gilman: Organic Chemistry, 2nd ed., pages 962,

group having 2 to 5, inclusive, carbon atoms. 963 (1943). Pub. John Wiley, New York. 

5. THE AZO COMPOUND HAVING THE FORMULA: 